Dinitrophenyl ester pesticides

ABSTRACT

2-Butyl-4,6-dinitrophenyl and e.g. alkyl mixed esters of aliphatic dicarboxylic acids, the esters having pesticidal activity including insecticidal and selective herbicidal activities.

United States Patent mi Pianka llll 3,714,230 Jan. 30, 1973 DINITROPHENYL ESTER PESTICIDES Inventor: Max Pianka, St. Albans, England Assignee: The Murphy Chemical Company Limited, Wheathampstead, St. Alban's, England Filed: July 24, 1969 Appl. No.: 844,627

US. Cl. ..260/479 S, 71/106, 424/313 Int. Cl. ...,C07c 69/34, C07c 69/40, C07c 69/60 Field of Search ..260/479 S Primary Examiner-James A. Patten Alt0rneyBacon and Thomas [57] ABSTRACT 2-Butyl-4,6-dinitrophenyl and e.g. alkyl mixed esters of aliphatic dicarboxylic acids, the esters having pesticidal activity including insecticidal and selective herbicidal activities.

17 Claims, No Drawings DINITROPHENYL ESTER PESTICIDES This invention relates to novel dinitrophenyl esters and to compositions prepared therefrom.

It has been found that certain novel dinitrophenyl esters have activities which make them of use in the fields of agriculture, horticulture and veterinary medicine. In particular, they have been found to show one or more of the following activities: herbicidal, insecticidal, acaricidal, aphicidal, fungicidal and nematicidal. The dinitrophenyl esters of the invention have the following structure:-

NO; I

in which A is CH=CH or (Cl-l where n is 0, or an integer from 1 to 6 and R is cyclic or acyclic, saturated or unsaturated aliphatic group which may be substituted with one or more of the following substituents: halogen atoms, nitro groups, amino groups, substituted amino groups, hydroxyl groups, carboxy or carbalkoxy groups, alkoxy or alkylthio groups, xanthyl groups and heterocyclic groups, or R is an unsubstituted or ringsubstituted heterocyclic, araliphatic or aryl group (including 2-t-butyl-4,6-dinitrophenyl), with the provisos that R is not methyl when A is CH=CH, and R is not 2-t-butyl-4,fi-dinitrophenyl when n is O. The invention also includes acid addition salts with inorganic or organic acids and salts with bases where appropriate.

R may, for example, be an alkyl group having 1 to 18, preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl isopropyl, butyl, octyl or decyl.

Compounds of the formula I may be prepared by reacting 2-t butyl-4,G-dinitrophenol, or a functional derivative (e.g. an alkali metal salt) thereof, with an acylating derivative of an acid of the formula R.O.CO.A.CO H 11 wherein R and A have the meaningsdefined above. Suitable acylating derivatives are acyl halides, especially chlorides, and anhydrides. An acid binding agent, such as pyridine, dimethylaniline or an alkali metal carbonate is preferably present in the reaction mixture. A solvent, such as diethyl ether, benzene or tetrahydrofuran, may be present if desired. When an alkali metal salt of the phenol is used, acetone or other ketone is a suitable solvent. 1

Compounds of the formula I particularly in which R is an alkyl group having 1 to 12 carbon atoms have a marked herbicidal activity, and may be used as total or selective herbicides. For example, compounds in which CO.A.C0.0R is ethyl fumaryl, methyl succinyl, methyl oxalyl or ethyl oxalyl may be used as selective herbicides on wheat and sugar beet crops. A pre-emergence application at the rate of 4.48 kg/ha gives good control of shepherds purse, groundsel and chickweed without damage to the crop. The propyl fumaryl compound gives similar weed control in rice at a rate of 3.36 kg/ha (post-emergence application). Rates of application are typically l.12-l1.2, preferably 2.24-5.6 kg/ha. Various modes of application, including preand post-emergence and soil incorporation, may be used.

Compounds of formula I particularly in which R is an alkyl group containing l-l2 carbon atoms are also notable for their nematicidal activity, and are thus potentially useful for the control of nematodes in soil and elsewhere. Examples of compounds having significant nematicidal activity are the isopropyl, pentyl, hexyl, heptyl and octyl fumarates, and the n-propyl and nbutyl succinates.

, Compounds of formula I particularly those where R is an alkyl group containing 1-12 carbon atoms are active against economically important insects e.g. Lucilia sericata, Boophilus decoloratus, A'edes aegypti and Musca domestica rendering the compounds useful for the control of insect pests in the agricultural, veterinary, horticultural and domestic fields. The compounds may also be of interest for the control of acaridae.

Examples of compounds possessing this activity include the butyl, iso-butyl, hexyl and heptyl fumarates, the methyl succinate and the ethyl oxalate.

in view of the above-mentioned activities, the invention also provides a herbicidal, nematicidal, insecticidal or acaricidal composition comprising a compound of formula I in combination with a suitable carrier or diluent. The carrier may be liquid or solid and designed to aid the application of the compound either by way of dispersing it where it is to be applied or to provide a formulation which can be made by the user into a dispersible preparation.

Liquid preparations thus include preparations of the compound in the form of solutions oremulsions, for example in non-aqueous solvents, which can be used on their own or be adapted to be made up with water or other diluents to form sprays etc; in such cases the carrier is a solvent or emulsion base free of undesirable toxicity under the conditions of use. Generally such preparations will include a wetting, dispersing or emulsifying agent. Aerosol packs may be prepared by using a gaseous or low-boiling propellant to expel the active compound or a solution thereof.

Solid preparations include dusts and wettable powders, granules, pellets and semi-solid preparations in the form of pastes. Such preparations may include inert solid or liquid diluents such as clays, which may themselves have wetting properties, and/or emulsifying,

wetting or dispersing agents; binding and/or adhesive agents may also be included. Solid preparations also include thermal fumigating mixtures wherein the compound is associated with a solid pyrotechnic composi tion such as a mixture of clay, lactose and potassium chlorate. 3 I

Compositions of particular importance are those suitable for preparing dips, sprays or drenches for external application to livestock, especially cattle for the control of parasitic insects such as ticks. Such compositions are suitably of the self-emulsifying liquid type in which the compound is associated with a non-aqueous carrier and an emulsifying or dispersing agent.

For the better understanding of the invention, the

I following examples are given by way of illustration only.

EXAMPLE 1 A. Preparation of n-pentyl fumaryl chloride Maleic anhydride (39.2 g., 0.4 mole) and pentan-l- 01 (35.2 g., 0.4. mole) were mixed at room temperature. After standing overnight the mixture was heatedfor 30 min. on a steam-bath. A solution .of thionyl chloride (37.5 ml.), in benzene (40 'ml.), was added and the resulting solution was heated under reflux for 18 hr.,

then distilled to give pentyl fumaryl chloride (61.4 g.),

The other chlorides specified'in Table 1 below were prepared similarly, except for ethyl fumaryl chloride and propyl-fumaryl chloride, for whose preparation a large excess of the appropriate alcohol was used.

B. Reaction of n-pentyl fumaryl chloride with 2-tbutyl-4,6-dinitophenol 2-t-Butyl-4,6-dinitropheno1 (16.8 g., 0.07 mole), potassium carbonate (4.93 g.) and acetone (70 ml.) were heated under reflux for 30 min. The resulting mixture was stirred and cooled to and n-pentyl fumaryl chloride (14.3 g., 0.07. mole) was added dropwise keeping the temperature between 0 and 5. The reaction mixture was then heated under reflux for 1% hr., cooled, and filtered. The volatile components of the filtrate were distilled off at -20 mm. on a steam-bath and the residue was-shaken with benzeneand 2N-sodium carbonate. The benzene solution was separated, washed with water, dried over sodium sulphate and the volatile components distilled off at 10-20 mm. on a steam-bath. The residue was crystallized from methanol to give 2-t-butyl-4,6-dinitrophenyl n-pentyl fumarate as fine white needles (13.2 g.), m.p. 69-70 (Found: N, 6,9, C,,1-l, N,O requires N, 6.9%).

The other alkyl fumarates listed in Table 11 were prepared similarly, using the appropriate alkyl fumaryl chlorides. 1

EXAMPLE 2 Preparation of 2-t-butyl-4,6-dinitrophenyl n-propyl succinate potassium carbonate (4.23 g.) and acetone (70 ml.) were heated under reflux for 30 min. The resulting mixture was cooled to 0 and n-propyl succinyl chloride (10.8 g., 0.06 mole) was added dropwise with stirring, keeping the temperature between 0 and 5. The reaction mixture was heated under reflux for 1% hr., cooled and filtered. The volatile components of the filtrate were distilled off at l0-20 mm. on a steam-bath.- The residue was shaken with benzene and ZN-sodium carbonate. The benzene solution was separated, washed with water, and dried over sodium sulphate. The volatile components were distilled off from the dried solution and the residue was crystallized from propan 2-ol giving 2-t-butyl-4,6-dinitrophenyl propyl succinate as pale yellow prisms (18.7 g.), m.p. 51-2 (Found: N, 7.2, CnHggNgOg requires N, 7.3%). v

The other alkyl'succinates listed in Table 11 were prepared similarly, using the appropriate alkyl succinyl chlorides.

EXAMPLE 3 Preparation of 2-t-butyl-4,6-dinitrophenyl ethyl oxalate 2-t-Butyl-4,6-dinitropheno1 (24.0 g., 0.1 mole), potassium carbonate (7.5 g.) and acetone (75 ml.) were heated under reflux for 30 min. The mixture was cooled to 5 and ethyl oxalyl chloride (15.1 g.) was added dropwise with stirring, keeping the temperature below 15. The resulting mixture was heated under reflux for 2 hr., cooled and filtered. The filtrate was distilled at 10-20 mm. on a steam-bath and the residue was shaken with a mixture of benzene and 2N-sodium carbonate. The benzene solution was separated,- washed with water, and dried over sodium sulphate. The volatile components of the dried solution were distilled off at 10-20 mm. on a steam-bath, and the v residue was crystallized from propan-Z-ol ml.) to

give the title compound (24.5 g.), m.p.83-84 (Found: N, 7.9, C H N O requires N, 8.2%).

2-t-Butyl-4,6-dinitrophenyl methyl. oxalate prepared similarly; its physical properties are shown in Table I1.

EXAMPLE 4 2-t-Butyl-4,6-dinitrophenol 14.4 g., 0.06 mole), (Found:N,10.0,C, H,,N O, requiresN,9.5%).

7 TABLE II Name of compounds, 2-t-butyl-4,6- Molecular W dmitrophenyl ester Description, solvent of crystallization formula Found Required Ethyl fumarate Cream needles, propan-2-ol C H N-0 n-Propyl fumarate Pale yellow needles CiiHlZNEOi 7 2 n-Butyl lumarate Cream prisms, methan0l CrsHzzNzOa 7 25 7 1 n-Ientyl fumarate White needles, methanol. Ci0H2-lN2Os 6. 9 6 n-Hexyl iumarate White prisms, methanoL. CauHzsNzOa 6. 6 0 n-Heptyl fumarate .de L'lHziNzOfl 6. 5 6 4 n-Octyl fumarate .do caramel a. a a 2 n-Nonyl fumarate. White needles, methanol CnlIazNzOa 6. 0 6 0 n-Deeyl fumarate Cream prisms, methanol and dlisopropylether. .CzrHuNzOa 5. 8 5 q n-Undecyl fumarate" Cream needles, methonoL. CzsiiasNz x 5 4 5 7 n-Dodeeyl fumarate. White prisms, methanol- CnllasNzOn 5:6 5 Isopropyl fumarate Cream needles, methan01. 111111019205 7 4 4 s-Butyl fumarate Fine cream needles, methanol (ImllnNzOn 7:2 7 I Isobutyl fumarate lalc yellow prisms, methanol (lmlhzNzUn 7. 2 7.

was

TABLE n- Continued v Analysis, percent H Name of compounds, 2-t-butyl-4,6- I Molecular dinitrophenyl ester Description, solvent of crystallization Hp, C. iii-{ formula Found Required Methyl succinate Prisms, propan-2-ol 82. 5-83 ClsHlSNzOB 7. 9 7, Ethyl succinate Pale yellow prisms, propan-2-ol 56-57 ClfiHQoNgOfl 7, 5 7 n-Propyl succinate Pale yellow prisms, propan-2-ol 51-52 CflHQZNQOB 7, 2 7 n-Butyl succinatencn Orange oil 1. 5163 ClBHzrNzOa 7. 05 7. 1 Methyl oxalate Pale yellow prisms, carbon tet 148. 5-149. 5 CmHuNzOs 8.05 8, 6 Ethyl oxalate Pale yellow prisms, propah-Z-ol 83-84 CuHmNzOs 7. 9 s. 2 Ethyl adipate White crystals, propan-ZoL. 70-71 CitH24N2Os 6. 5 7,1 2-t-buty1-4,6-dinitropheny1 adipa White prisms benzene/petrol 179-180 CgtH N O 9,5 9, 32

EXAMPLE 5 This example illustrates the herbicidal utility of the compounds of the invention. The compounds were tested'for herbicidal activity against common weeds by pre-emergence, incorporation and post-emergence box tests.

The methods of testing the compounds for herbicidal activity were as follows. Control experiments were carried out in all tests.

Pre-emergence box tests In boxes were sown the following common weeds: shepherds purse (Capsella bursa pastoris), groundsel (Senecio vulgaris), chickweed (Stellaria media), rye grass, annual meadow grass, dock (Rumex spp.), fat hen (Chenopodium album), and the following crops: cabbage, carrots, wheat, sugar beet, rice.

The compounds to be tested were formulated as follows:

g. of the active compound and 10 g. of a blend of non-ionic and ionic emulsifying agents Agrilan A, sold by Lankro Chemicals Limited, were made up to 100 ml. with heavy naphtha. This solution was diluted with the appropriate quantity of water and applied to the boxes at a rate of 4.48 kg. of active compound in 181.6 liters of water per hectare on the day of sowing. Artificial rain equivalent to 6.25 mm was then applied. The containers were kept under glass at about 14C. and watered as necessary. The effect of this treatment was assessed after 21 days. For determination of the herbicidal activity against weeds, the number of live seedlings of each weed series was assessed and the percentage control was calculated, allowing for natural mortality.

Incorporation box tests 5 cm deep seed trays were filled with soil and were sprayed on the surface with the dilution of the active compound at the rate of 4.48 kg/ha. The soil was then poured through a funnel into a large drum. The lid was placed on the drum and the drum was shaken to mix the soil. The soil was transferred to the trays. In the trays were then sown the standard weeds and the crops listed above, and the effect of the treatment was assessed after 21 days.

Post-emrgence box tests in boxes were sown the standard weeds and the crops listed above. When the seedlings had reached the second true leaf stage (about 2 to 3 weeks), the formulation of the active compounds was diluted with the appropriate quantity of water and applied to the seedlings at the rate of 4.48 kg of the active compound in 363.2 liters of water per hectare.

The results of the herbicidal tests are shown in Table III, wherein the headings Pre., Incorp., Post. represent pre-emergence, soil incorporation and postemergence.

Sometimes the number of live seedlings in the treated boxes was greater than that in the untreated boxes. In assessing the control of the individual species, this would have been expressed as no control. It was therefore considered advisable to calculate the total percentage control as a percentage on the sum total of the live weed seedlings in the treated containers relative to the untreated containers. These percentage controls may differ considerably from the arithmetical means calculated from the assessments of the controls of the individual species.

TABLE III.HE RBICIDAL ACTIVITY (PERCENT) Shepherds purse Groundsel Chickweed Rye grass Pre. Incorp. Post. Pre. Incorp. Post. Pre. Incorp. Post. Pre Incorp. Post.

Alkyl tumarates:

Ethyl 100 96 100 100 74 100 90 91 100 6t 100 100 100 71 96 100 91 100 28 84 100 100 100 91 100 100 76 100 78 89 43 100 100 100 96 100 100 78 100 54 53 100 100 100 91 100 100 91 100 58 63 43 100 100 100 96 100 100 83 100 72 47 59 100 100 100 96 100 100 100 190 72 56 76 97 100 68 100 86 38 98 0 14 9 97 100 100 84 100 97 59 100 0 0 44 87 97 100 84 100 100 55 100 0 0 23 85 100 95 26 100 86 100 0 0 17 96 100 96 91 100 100 87 99 19 25 6 96 100 100 83 96 44 90 40 0 7 100 100 100 97 86 100 14 0 37 Annual meadow grass Dock Fat lien Total control Pre. Incorp. Post. Pre. Incorp. Post. Pre. Incorp. Post. Pre. Incorp. Post.

76 100 66 91 87 90 75 72 81 62 73 74 80 86 62 75 72 82 (i7 80 b3 73 .2 46 41 G7 87 83 71 83 75 69 76 63 yl 73 70 Alkyl oxalates:

Methyl 93 87 Ethgll 83 97 Alkyla 'patezEth 53 69 Table ivias'aizies' the p'hytotoxicity of the compounds against some common crops, representing the ratio of the fresh weight of the treated plants to the fresh weight of the untreated plants, expressed as a pe rcentage. Thus. 100 indicates no phytotoxicity and O indicates crop death.

Preemergence box tests Cabbage Carrots Wheat Sugar beet 2.24 kg./ 4.48 kg./ 2.24 kg./ 4.48 k 2.24 kg./ 4.48 kg./ 2.23 kg./ 4.48 kg./ 1.68 kg./ 3.36 kg./ 5.03 kg./ ha. ha. ha. ha. ha. ha. ha. ha. ha. ha. 112..

Post emergence box tests Rice Fumarates:

Ethyl 0 0 10 41 100 100 100 100 4 07 p 89 5 Propyl 12 1 02 100 100 100 100 100 100 00 Succinate:

Methyl 0 1s 00 18 100 100 100 100 so 86 Oxalates:

Methyl ,0 0 05 as 100 100 100 100 0 0 Eth 12 46 44 100 100 100 100 0 0 Adipate: Ethyl 50 12 05 85 100 100 100 1000 85 13 EXAMPLE 6 g then dosed orally with the compound. Systemic activity v is assessed b notin the time taken to re el larvae from This example demonstrates the insectlcidalactivity the strike y g p v of the compounds of the invention. v n

The following test insects were used: 3. Compounds are screened against immature Aedes Boophilus decoloratusthe blue tick I aegypti; third to fourth instar larvae inwater are treated Lucilia sericata-the blow fly responsible for strike with l0 ppm for 24 hours.

in sheep n Aedcs aegypti the mosquito vector of yellow fever Musca domestica-the common house fly Each insect necessitated the use of a different mode of testing, as follows:

l. Boophi'lus decoloratus, blue tick larvae, are held for 24 hours in close contact with a 0.1 percent solution of the substance under test, absorbed "on filter paper, after which time mortality is assessed.

4. Female house flies, (Musca domestica,-) are used, (the males are more susceptible). These are dosed topically with lal of a'0.l percent solution. Mortality is assessed after 24 hours.

The results of testing a variety of the compounds of the invention on the four above-mentioned insects are minimum lethal concentration.

TABL E vQi NSEQTIC I DAL ACTIVITY Mammalian Aedes Boophilus Lacilia toxicity Ester of 2-tbutyl 4,6-dinitro.- aegypti decoloratus sericata Musca (mice) in phenol larvae larvae larvae domertica mgJkg.

Acute oral MLC, MLC, MLC, LDw, LDsop.p.m. percent percent percent approx.

Ethyl oxalate 10 0. 0007 0.006 0.04 Ethyl fumarate 10 0. 003 0.0125 0. 04 400 Butyl ltmarate 10 0 025 0. 006 0. 04 400 Pentyl fumarate 10 0 025 0. 0125 0. 04 200 Hexyl fumarate- 10 0 05 '0. 006 0. 04 1, 600 Heptyl Iumarate 10 0 05 0. 006 0. 05 1, 600 Octy1iumarate I 10 0 05 0. 0125 0. 06 1, 600 Sec-butyl tumarate. 10 0. 1 0. 0125 0. 04 400 Dodecyl t'umarate l0 0. 1 r 0. 006 0. 06 1,'600' Isobutyl fumarate l0 0. 1 0. 006 0. 1 800 shown in Table V. The abbreviation ML'C stands for TABLE V.-INSECTICIDAL ACTIVITY (ominued Mammalian Aedes Boophilus Lucilia toxicity Ester i Z-t-butyl 4,6-d1nitro-. aegypti decolomlus sericata Musca (mice) in phenol larvae larvae larvae domestz'cu mgjkg.

Acute oral MLC, MLC, MLC, LDro, LDW- p.p.m. percent percent percent approx.

D ecyl rumara'f 0. 1 0. 006 0. 1 1, 600 Nony1fumarate 10 0.1 0. 0125 0.1 1, 600 Undeeyl fumarate. 10 0. 1 0.0125 0. 1 1, 600 Bis fumarate 10 0. 002 0. 041 600 Methyl suceinate 10 0. 006 0. 0125 0. 04 100 Ethyl succinate 10 0. 025 0. 006 0. 04 50 Butyl succinate 10 0. 1 0. 006 0. O4 50 Propyl succinate. 1O 0. 1 0. 006 0.05 50 Ethyl adlpate 10 0. 025 0. 006 0. l 400 The ethyl oxalate ester was tested against Blatella I 5 TABLE VI] germanica and found to have a minimum lethal concentration of 536 mg/sqm.

EXAMPLE 7 The nematicidal activity of the compounds of the invention was tested against Panagrellus, a free-living nematode. The test procedure was as follows:

Panagrellus was cultured on an oatmeal medium and the nematodes, of all age groups, were suspended in water to form a concentrated suspension. 1 ml of this suspension was added to an aqueous medium containing one of a number of test compounds at a concentration of 500 ppm. This suspension was then further diluted as required to give concentrations of test compound of 300, 100 and 30 ppm.

After 48 hours the dead and live nematodes were counted visually under a microscope. The percentage control was then assessed, after allowing for natural mortality.

The results are shown in Table VI.

TABLE VI Ester of 2-t-butylcontrol at (ppm) 4,6-dinitrophenol 300 100 30 ppm Fumarates Ethyl 80 0 n-iropyl 60 25 i0 n-Butyl 90 70 15 Pentyl 100 100 60 Hexyl 100 95 40 l-leptyl 100 100 so Octyl 100 100 25 lsopropyl 100 100 Succinates Methyl 80 75 6O Ethyl 100 95 46 n-Propyl 100 W0 95 n-Buty 100 I00 65 Oxalates Ethyl 95 95 35 EXAMPLE 8 Compounds according to the invention were tested for activity against root knot nematodes (Meliodogyna spp) and stem nematodes (Ditylenchus dipsaci).

The compounds were applied by soil incorporation just before planting seeds of the test plants (cucumber for root knot nematode, and alfalfa for stem nematode). The test plants were assessed for disease incidence two weeks after planting.

The effectiveness of each compound is indicated in Table VII on an arbitrary scale running from 5 (100 percent control) to 1 (N0 control of disease), while indicates that the plant died or was severely injured and a reading was not possible.

Ester of Z-tert. butyl- 4,6dinitrophenol Activity Rating Root nematode Stern nematode (22.4 kglha) (44.8 kg/ha) Fumarates: n-Pentyl 5 3 n-Hexyl 4 (T) n-Octyl' '5 5 n-Undecyl 5 2-tert-butyl-4,6- dinitrophenyl 5 4 Succinates: Ethyl 5 5 Adipates: Ethyl 5 l 2-tert-butyl-4,6- dinitrophenyl 4 1 EXAMPLE 9 The activity of the compounds according to the invention was tested against Aphis fabae by contact application, the host plant being broad beans. Treatment was applied by a dipping technique, and the percent control was assessed 48 hours after treatment. The

results are shown in Table VI.

TABLE Vlll Ester of Z-tert-butylcontrol at (ppm) 4,6-dinitrophenol 300 100 Fumarates:

lsopropyl 90 n-Butyl 83 58 n-Hexyl 75 38 n-Heptyl 77 66 n-Octyl 75 68 Succinates:

Ethyl 84 n-Propyl 97 74 n-Butyl 92 54 EXAMPLE 10 The activity of compounds according to the invention was tested against schradan-resistant red spider, Tetranychus telarius. Treatment was applied by a dipping technique and the percent control was assessed 48 hours after treatment. The results are shown in Table IX.

EXAMPLE 11 The activity of the compounds of the invention was tested against the Mexican bean beetle (Epilachna Varivestis) by a stomach poison test.

The host plants were sprayed with a formulation of the compound at the desired concentration, allowed to dry, and subsequently infested with the test insects. The percentage control was assessed after 48 hours. The results are shown in Table X.

' The compounds of the invention were tested for activity against the Two Spotted spider mite (Tetranychus urticae) I The mites were sprayed with a formulation of the toxicant in a co-solvent, wetting powder and water, at the desired concentration. A standard spray tower and an atomizer sprayer were used. The percentage mortality of the test mites was assessed 48 hours after treatment. The results are shown in Table Xl.

TABLE X] Enter of 2-tert.butyl- Control at (ppm) 4,6-dinitrophenol Fumarates: Ethyl 99 99 89 99 45 78 n-Pentyl 99 99 99 66 56 88 n-Hexyl 99 99 99 88 65 76 n-Hept l 99 99 99 89 97 n-Octy 99 88 '78 99 82 n-Undecyl 99 99 89 89 87 Succinate:

Ethyl 99 99 99 98 55 EXAMPLE 13 .The compounds of the invention were tested for activity against the Milkweed bug (Oncopeltis fasciatus) by themethod employed in Example 12. The results are shown in Table XII. i

TABLE X!" Enter of 2-tert.butyl- Control at (ppm) 4,6-dinitrophenol I000 500 250' 100 50 Furnarater: Ethyl 99 96 52 i 82 52 n-Pentyl 99 89 99 98 l n-Hexyl 99 99 99 33 n-Ocgl 89 79 32 2| n-Un ecyl v 99 99 98 98 67 Succinates: I Ethyl 99 99 95 82 Adipate: Ethyl 99 ll 20 I claim: 1. A compound selected from the group consisting of the compounds of the formula 0. CO.A. CO. 0R

(CHs)aC NO in which A is chosen from the group consisting of CH=CH and (CH,),,--' where n is chosen from the group consisting of 0 and integers from lvto 6, and R is a group chosen from the group consisting of alkyl groups having 1 to 18 carbon atoms, with the proviso that R is not methyl when A is -CH=CH.

2. Compounds as claimed in claim 1 in which the group R is selected from the groupconsisting of alkyl groups having 1 to 12 carbon atoms.

3. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl n-butyl succinate.

4. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4;6-dinitrophenyl methyl oxalate.-

5. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl ethyl oxalate.

6. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl ethyl fumarate.

7. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,o-dinitrophenyl propyl fumarate.

8. Compounds as claimed in claim 1 whereinsjaid compound is 2-t-butyl-4,6-dinitrophenyl isopropyl fumarate.

9. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl n-butyl fumarate.

l0. Compounds as claimed in claim 1 wherein said 7 compound is 2-t-butyl-4,6-dinitrophenyl isobutyl fu-' marate.

ll. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,-dinitrophenyl pentyl fumarate. 1

l2. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl hexyl fumarate. I i

- l3. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6 dinitrophenyl heptyl fumarate.

' l4.-Co'mpounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl octyl fumarate. t

l5 Compounds as claimed in claim 1 wherein said compound is 2tbutyl-4,6-dinitrophenyl'ldecyl fumarate. I 16. Compounds as claimed in claim 1 wherein said compounds is 2-t butyl-4,o-dinitrophenylmethyl succinate. I

l7. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,-dinitrophenyl n-propyl succinate. 

1. A compound selected from the group consisting of the compounds of the formula in which A is chosen from the group consisting of -CH CH- and -(CH2)n- where n is chosen from the group consisting of 0 and integers from 1 to 6, and R is a group chosen from the group consisting of alkyl groups having 1 to 18 carbon atoms, with the proviso that R is not methyl when A is -CH CH-.
 2. Compounds as claimed in claim 1 in which the group R is selected from the group consisting of alkyl groups having 1 to 12 carbon atoms.
 3. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl n-butyl succinate.
 4. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl methyl oxalate.
 5. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl ethyl oxalate.
 6. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl ethyl fumarate.
 7. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl propyl fumarate.
 8. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl isoprOpyl fumarate.
 9. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl n-butyl fumarate.
 10. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl isobutyl fumarate.
 11. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl pentyl fumarate.
 12. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl hexyl fumarate.
 13. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl heptyl fumarate.
 14. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl octyl fumarate.
 15. Compounds as claimed in claim 1 wherein said compound is 2-t-butyl-4,6-dinitrophenyl decyl fumarate.
 16. Compounds as claimed in claim 1 wherein said compounds is 2-t-butyl-4,6-dinitrophenyl methyl succinate. 